Novel cyan-dye forming coupler

ABSTRACT

A class of cyan-dye-forming Alpha -naptholic couplers having an alkylthio, an alkysulfinyl, or an alkysulfonyl ballasting group attached onto the Beta -naptholic ring; elements and emulsions containing said couplers and a method for improving color photographic images by utilizing said couplers.

United States Patent [191 Fernandez Jan. 15, 1974 1 NOVEL CYAN-DYEFORMING COUPLER [75] Inventor: Jose M. Fernandez, Rochester, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: June 2, 1972 [21] Appl. No.: 259,065

[52] US. Cl 96/100, 96/3, 96/74 [51] Int. Cl G03c H40 [58] Field ofSearch 96/100, 56.6, 55,

[56] References Cited UNITED STATES PATENTS 2,356,475 8/1944 Schinzel96/100 2,362,598 11/1944 Vittum et a1, 96/100 3,458,315 7/1969 Loria96/55 3,620,745 11/1971 Seymour 96/55 Primary Examiner-Norman G. TorchinAssistant ExaminerRichard L. Schilling Attorney-Robert W. Hampton et a1.

[57] ABSTRACT 28 Claims, N0 Drawings The present invention relates to anew class of -naphtholic compounds, particularly {3 ringsubstituteda-naphtholic couplers capable of reacting with oxidized color developingagent to form a photographic dye, silver halide emulsions containingsuch compounds, corresponding color photographic elements and a methodfor obtaining improved color photographic images.

By way of background, colored photographic images are generally obtainedin the art by coupling a silver image development by-product (i.e.,oxidized aromatic primary amino developing agent) with a color-formingcoupler compound. The subtractive process of color formation isordinarily employed and the usual resulting cyan, magenta or yellowimage dyes are complementary to the primary colors. Coupler compoundsemployed to produce cyan photographic dyes, for instance, are generallyof the phenolic or a-naphtholic type. A majority of such couplers areknown and described as four-equivalent couplers, and are characterizedin requiring the development of four lightexposed silver halidemolecules in order to obtain one molecule of dye. Also widely used areso-called twoequivalent couplers having a non-chromophoric coupling offgroup substituted in'coupling position and requiring the development ofonly two exposed silver halide molecules during development to obtainone molecule of dye. Known two-equivalent couplers and method for theirutilization are disclosed, for instance, in US. Pats. Nos. 3,458,315 and3,227,155 of Loria and Loria et al. respectively.

Suitability of an organic compound as 'a color photographic coupler,however, depends upon more than general reactivity. Consideration mustalso be given to the color balance, contrast, grain size and generalsharpness of the dye images obtained. A coupler should also be stableand produce stable photographic dyes having precise spectral absorptioncharacteristics upon reaction with oxidized developer.

Successful couplers also must possess a number of important ancillarycharacteristics. It is-desirable, for instance, to utilizenon-diffusible couplers which require minimal amounts, or nohigh-boiling coupler solvent in order to obtain thinner and more durablephotographic elements and betterimage resolution. Itis also importantthat non-diffusible couplers be capable of precise incorporation into asilver halide emulsion without adverse effects on emulsion viscosity,adhesion characteristics, or unity of the emulsion during modernhigh-speed multilayer application onto a film backing.

Including antihalation and gelatin interlayers, up to eight or moreseparate layers may be-applied to afilm base to obtain a modern colorphotographic element (ref. KirbOthmer, Vol. 5', pages 812-845,Encyclopedia of Chemical Technology (1950). For this reason,coupler-induced changes in the physical properties of a coatingmay wellbe as important as coupler reactivity with oxidized developer.

Undesirable changes in viscosity are sometimes traceable to particularcouplers or additives such as wetting agents etc., and these changes arecapable of directly affecting thecoating characteristics of thephotographic emulsion. This fact is indicated, for instance, on page 250of the test by Zelikman and Levi, entitled Making and CoatingPhotographic Emulsionsi" The Focal Press (1964).

A still further need exists in the art for non-diffusible,

coupler-type intermediate or precursor compounds to which it is possibleto releasibly attach various functionally useful groups such asdiffusible photographic dyes suitable for a diffusion transfer system.

The above-listed features are not necessarily complete and are sometimesincompatible since the color photographic technology of recent years iscomplex and functionally interrelated. In fact, some couplercharacteristics considered advantageous in earlier photographic art maynow even be considered undesirable.

For the above reasons, it is necessary to discover new compounds havingutility as couplers, and new color photographic elements efficientlyutilizing such compounds for color photographic purposes.

Generally speaking, the prior art fails to recognize particularfunctional significance in the available B- ring positions ofa-naphtholic cyan dye-forming couplers as a class. As a result, theamount and direction of chromatographic shift, the solubility andstability of such substituted couplers and of their corresponding dyesare essentially unpredictable, at best.

It is an object of the present invention to obtain a new class ofcompounds suitable as cyan dye-forming couplers for color photographicpurposes and as precursors for obtaining non-diffusible,diffusible-dyecarrying coupler-type compounds suitable for colordiffusion transfer systems.

It is another object of the present invention to provide new compoundswhich readily and efficiently react with oxidized color developer toproduce heatand light-stable cyan dyes suitable for modern colorphotographic purposes in photographic emulsions and elements.

his a still further object to obtain a new class of ballasteda-naphtholic cyan dye-forming couplers which are easily incorporatedinto a color photographic element, particularly into a colorphotographic emulsion thereof while usingminimal amounts, or optionally,no high-boiling coupler solvent at all.

These and other objects of the invention are obtained by utilizing aclass comprising a non-diffusible a-naphtholic cyan dye-forming couplerwith an alkylthio, alkylsulfonyl, or alkylsulfinyl substituent having atleast 12 carbon atoms substituted in the [3 ring of the a-na'phtholiccoupler.

Compounds of the above type are further conveniently described in thefollowing formula:

wherein -(NAOL) is an unballasted or lightly ballasted a-naphtholic cyandye-forming coupler moiety; R is an alkyl group, inclusive of straightand branched chain alkyls, having 12-22 carbon atoms and preferably13-18 carbon atoms (e.g. S-pentyl-heptyl, ntridecyl, n-octadecyl, anddocosyl); and -(L) represents S-,

wherein R, and L are defined as above;

R is a hydrogen atom, a halo group such as a chloro, an amino group,including an alkylamino group having one to 12 carbon atoms in the alkylmoiety (e.g., N-methylamine, N-dodecylamine); an alkyl carbonyl group of2-l 2 carbon atoms (e.g. methylcarbonyl, n-butyl carbonyl andnundecylcarbonyl); an arylcarbonyl group such as an unsubstitutedor asubstituted-phenylcarbonyl or a naphthylcarbonyl group in which ringsubstituent groups total zero to 12 carbon atoms, including achlorophenylcarbonyl group, an alkoxyphenylcarbonyl group having 1-2alkoxy substituent totaling zero to 12 carbon atoms or analkylphenylcarbonyl group having 1-2 alkyl substituents totaling -12carbon atoms (e.g. dimethylphenylcarbonyl, chlorophenylcarbonyl anddi-t-amylphenylcarboy R is also defined as a carbamyl group of theformula in which R is defined as a hydrogen atom or an alkyl group notexceeding three carbon atoms and preferably one to two carbon atoms(e.g. methyl, n-propyl) and R is defined as a hydrogen atom; an alkylgroup not exceeding 18 carbon atoms and preferably one to 12 carbons; anaryloxy alkyl group such as a phenoxy alkylor a naphthoxyalkyl group, anarylalkyl group such as a phenylalkyl-or a naphthyalkyl group, in whichthe alkyl moieties contain one to four carbon atoms (e.g., methyl,n-octadecyl, ndodecyl, 2,4-di-t-amylphenoxy-methyl, 2-methylcarbonamidophenyl butyl and 2-methylcarbonamidophenylethyl);

R is also defined as an aryl group such as phenyl, naphthyl including asubstituted aryl group such as a phenyl group or a naphthyl group havingas substituents a member of not more than 16 carbon atoms and preferablytotaling less than 12 carbon atoms such as one or more carboxy, alkoxyor alkyl-sulfonyl group (e.g., n-hexadecylsulfonylphenyl,3,5-dicarboxyphenyl, n-hexadecyloxphenyl, n-decyloxyphenyl); alsodefined as a carboncontaining heterocyclic group having a 5-6 memberedheterocyclic ring nucleus with at least one hetero-nitrogen, oxygen orsulfur atom in the nucleus such as a pyridinyl, a pyrimidyl, or aquinolinyl group;

R is defined as a hydrogen atom;

an amino group, including an N-alkylamine group in which the alkylmoiety contains not more than 10 carbon atoms as a coupling off groupsuch as a halo group (e.g. chloro or fluoro), a thiocyano group, anacyloxy group such as an alkoyloxy group of two to 10 carbon atoms, oran aroyloxy group such as a phenylcarbonyloxy group; e.g.

an alkoxy group or its sulfur analog having an alkyl moiety of one to 10carbon atoms (e.g. decyloxy, decylthio); as an aryloxy or an arylthiogroup (e.g. phenoxy, naphthoxy, phenylthio, n-decylcarbamylphenylthio,methylcarbamylphenoxy); as a heterocycloxy group or its thioanalog inwhich the heterocyclic moiety has a 5-6 membered heterocyclic ringnucleus with at least one hetero-nitrogen, oxygen or sulfur atoms, andpreferably containing 1-4 hetero-nitrogen atoms (e.g. a tetrazoyloxy, atriazinyloxy, a triazolyloxy, a tetrazolylthio, a benzothiazolylthioetc.);

as a sulfo group;

as an aryl azo radical of the formula in which R is defined as an arylgroup such as a phenyl group,

or a naphthyl group including substituted aryl such as analkylcarbonylphenyl, an alkoxycarbonylnaphthyl or an alkoxyphenyl groupin which the alkyl and alkoxy moieties contain one to 13 carbon atoms(e.g. p-butoxyphenyl, 2-n-propylcarbonylphenyl, and3-octyloxycarbonylphenyl); R being further defined as acarbon-containing heterocyclic group having 5-6 membered heterocyclicring nucleus with at least one hetero-nitrogen, oxygen or sulfur atoms,and preferably containing 1 to 4 hetero-nitrogen atoms. Such groupsinclude, for instance, a l-phenyl tetrazolyl, a triazinyl, a triazolyl,a thiadiazolyl, a benzoxazolyl, a benzotriazolyl, a benzothiazolyl, apyrimidyl, a pyridinyl and a quinolinyl group;

R as a coupling-off group also includes a sulfonamido group such as aradical of the formula which is wholly or partly displaceable uponreaction with oxidized color developing agent; also included within theabove definition are radicals of formula III in which R represents a dyeor dye precursor inclusive of an azo, an azomethine, an indoaniline, anindophenol, or an anthioquinone dye moiety; also included are leuco dyesor shifted dyes which will shift hypsochromically or bathochromicallywhen subject to a different environment such as a change in pH. Suchgroups are exemplified, for instance, in copending US. Ser. No. 176,751filed Aug. 31, 1971 and U. S. Ser. No. 176,752 also filed Aug. 31, 1971and now abandoned. R is also more specifically defined as an alkylgroup, inclusive of straight or branched alkyls of one to carbon atomsexemplfied by methyl, isopropyl, and ndecyl, also as an aryl group suchas a phenyl or a naphthyl group, inclusive of phenyl, naphthyl, andsubstituted phenyl or substituted naphthyl groups in which thesubstituted aryl ring has at least one substituent such as an alkylgroup of one to 10 carbon atoms, an alkoxy group of one to 10 carbonatoms, an amino, a nitro, a carboxy, a halo, an arylazo group such as aphenylazo or naphthylazo group, a heterocycloazo such as a pyrazolinogroup, carbamyl group such as an N-phenyl carbamyl, aN-heterocyclocarbamyl such as a N-triazinyl-or an N-pyrazolino-carbamyl,and an alkyl-substituted carbamyl of two to 10 carbon atoms (e.g.N-propyl carbamylphenyl, p-aminophenyl, p-nitrophenyl, 4-amino naphthyl,3-methyl-4-nitrophenyl, 2- nitrophenyl, S-carbamylphenyl etc.).

Suitable diffusible a-naphtholic cyan dye-forming coupler moietiesfalling within the above general definition of -(NAOL) are described,for instance, in US.

Pats. Nos. 2,113,329 and 2,252,718 of Mannes et a1.,

3,002,836 of Vittum et al., US. Pat. No. 3,253,924, US. Pat. No.3,458,315 (e.g. couplers 1, 4-7, 19-23, 25-29 and 39) and in US. Pat.No. 3,311,476 of Loria (coupler 6). Such patents, however, are notlimitative, but merely exemplify some of the unballasted or lightlyballasted coupler moieties of the type to which the [3 ring substituent(ref. formula 1) may be attached.

For purposes of describing the present invention, it is understood thatthe term coupling-off group defines a substituent group attached at theNo. 4-coupling position of an a-naphtholic cyan dye-forming coupler,said substituent group being split off or released for instance, uponcoupler reaction with oxidized developing agent.

The term lightly ballasted a-naphtholic cyan dyeforming coupler moietydefines a color photographic coupler group having at least oneadditional ballasting substituent group other than a [3 ringsubstituent, said additional ballasting group or groups favoringnon-diffusibility of the coupler in a gelatino silver halide emulsion orcontiguous gelatin layer without causing substantial loss in solubilityin the corresponding fully ballasted non-diffusible coupler (i.e., thefl-ring substituted coupler) in the usual coupler solvents (ref.

infra). I

Substituted compounds of interest are obtainable, fo instance, byreaction of commercially available 1,7- dihydroxy naphthalene with analkyl mercaptan in the presence of p-toluenesulfonic acid to obtain adesired 7-alkylthio derivative. This compound, in turn, can be convertedto the l-acetoxynaphthalene by reacting, with acetic acid anhydride,then oxidized to the corresponding alkylsulfo or alkyl sulfinyl. Thel-acetoxy derivative is then subjected to a Fries rearrangement toobtain a corresponding l-hydroxy 7-a1kylsulfonaphthyl derivative. Thegeneral reaction mechanism is demonstrated as follows:

1) 0 1r OH HO nolulasn HCXBHIYS 5 p-toluenesuHonic acid n C s cm-b-o--cm0 C OCH:

2O (3) O OCOCH: (I)COCHJ 11 1sHa1- S n C isHuSO 3 0 II l 0 ll- Theproduce of equation (3) (pag. 11) can be rearranged as follows:

(refljbur. Pli arm. Soc. of Japan 74, pg 154-6 (1954)).

Corresponding 1,5 and 1,6 isomers of the above compounds are alsoobtainable to form the corresponding dihydroxy naphthylene precursors(ref. Richter Lexikon Der Kohlenstoffe Vubindungenz, 3rd ed.; Vol.11,page 1411 (1911) Z-Equivalent 4-sulfonamido substituted couplersincluded within the present invention are conveniently obtained, forinstance, by reacting the corresponding a-naphthol 4-amine with thedesired aryl sulfonyl halide.

The following compounds are listed in Table 1 with respect to Formula 11to illustrate a group falling within the scope of the present invention:

(In OH (IV) on TABLE II Compound number R L L R R3 25. CH3(CHz) S H H 26CHa(CH2)11 (H) H H 27 CHa(CH2)u I H H 28 r CIIz(CHz')n- -S- H -N=N--OCH3 2U CH3(CHz)11 s- H H 30 CHa(CHz)n- 4') H ll -N=N OCH3 31.CH3(CHZ)11 -S CzHs COOH H C O-N- OOH 32. CHa(CHz)11 S C O-NH-CHzs n( llsHuflil 33 CH3(CHz)11 -S Sameasabove H 34 CHa(CHz)n ('3' CzHs COOH HJOOH 35. CH3(CH2)12 1; g H

H O CCH3 311.. (,llzflllldlz C1-- The ballasted non-diffusible type cyancouplers of the present invention can be usefully incorporated into aphotographic element as part of a photographic silver halide emulsionlayer or contiguous thereto. This is most conveniently accomplished byinitially dissolving the coupler into a high-boiling and/or one or morelowboiling organic solvents. The resulting solution is then dispersedinto a gelatin solution with the aid of an emulsifier, and this couplerdispersion is 'set, noodled, washed and then melted and dispersed into alightsensitive silver halide gelatin dispersion and thereafter coatedonto a film support. Suitable solvents and techniques for this purposeare disclosed, for instance, in US Pats. Nos. 2,949,360, 2,801,171,2,322,827 and 2,304,939 and on page 107 (Section 11) of ProductLicensing Index, Vol. 92, Publication 9232; (Dec. 1971).

Suitable light-sensitive silver halide gelatin emulsions and referencesdescribing their preparation and sensitization, .which are suitable foruse in preparing photographic elements within the present invention, aresummarized on page 107 (Section 1 and Ill) and pages 108-9 (Section XV)of Product Licensing Index, Vol.

92, Publication 9232 (Dec. 197] Such emulsions can 1. A support layerincluding cellulose acetate film, polystyrene film, polyethylene film,polypropylene film, poly (ethylene) terephthalate film, etc. or asotherwise described, for instance, on page 108, Section X of ProductLicensing Index, Vol 92, Publication 9232 (Dec. 1971). Such supports canoptionally be electronbombarded at a contact angle of less than 45 orotherwise treated (ref. U.S. Pats. Nos. 3,220,842, 3,117,865 and BelgianPatent 671,661);

2. An antihalation layer attached to the support layer such as adye-containing gelatin starch, etc., as described, for instance, inGlafkides Photographic Chemistry, Vol. 1, pages 470-471, Arrowsmith Ltd.1958;

3. One or more, preferably three types of lightsensitive differentlysensitized silver halide emulsion layers coated onto the support; thelayers comprise (a) a single or double coated red-sensitized layercontaining at least one cyan dye-forming coupler of the type defined informulae l-II (supra). (b) A green-sensitized emulsion layer containingat least one S-pyrazolonemagenta-dye-forming coupler (ref. 823-4, Volume5, Kirk-Othmer, Encyclopedia of Chemical Technology (1964), also U.S.Pats. Nos. 2,600,788, 2,908,573, 2,895,826, 3,519,429, 3,227,554,3,062,653 and 2,983,608); and (c) a blue-sensitized layer containing anopen-chain yellow dye-forming ketomethylene coupler (ref. pages 822-23,Volume 5, Kirk-Othmer, Encyclopedia of Chemical Technology (1964), alsoU.S. Pats. Nos. 2,875,057, 2,895,826, 2,908,573, 3,265,506, 3,384,657,3,408,194 and 3,447,928); a Carey-Lea filter layer is optionallyinterposed between the blueand greensensitized layers.

Suitable light-sensitive silver halide emulsion and referencesdescribing their preparation and chemical sensitization thereof aresummarized, for instance, on page 107 in Section I and III of ProductLicensing Index, V0. 92, Publication 9232 (Dec., 1971 and includeemulsions of silver chloride, silver bromide, silver chlorobromide,silver bromoiodide, silver chlorobromiodide and silver chloroiodide.

4. One or more gelatin spacer layers between the light-sensitiveemulsion layers or the emulsion layers and Carey-Lea filter layer asabove described; and

5. A protective water-permeable overcoat layer, such as gelatin,poly-N-vinyl lactam, gum arabic, hydrophilic copolymer ofN-acrylamidoalkyl betain (ref. U.S. Pat. No. 2,833,650), celluloseethers and esters, alkali soluble polyvinyl phthalate (ref. U.S. Pat.No. 2,798,004); also water-soluble polymers having varying degrees ofsolubility, such as polyvinyl alcohol (optimally with surfactant),polyvinyl pyrrolidone polyalkylene oxides, polyvinyl alcohol and itsderivatives such as partial esters, ethers and acetals exemplified byhydrolizyed polyvinylacetate, polyvinyl acetaldehyde acetal, polyvinylbutyraldehyde acetal, polyvinyl osulfobenzaldehyde acetal. polyvinyldisodium 2.4 disulfobenzaldehyde acetal; and water-soluble copolymersand interpolymers exemplified by copoly (methyl vinyl ether/ maleicanhydride), copoly (acrylic acid/- methacrylic acid ethyl ester-maleicanhydride) and copoly (maleic anhydride/acrylic acid/vinyl acetate. Theovercoat may conveniently contain an aldehyde scavenger such asdescribed, for instance, in U.S. Pat. Nos. 3,236,652, 3,287,135,3,220,839, 2,403,927 and British Patent 623,448, and other ingredientssuch as buffering agents (e.g., an acidic or basic material), andultra-violet light absorbers such as 2,2'-d-hydroxy4,4'-dimethoxybenzophenone, 4,4'-diazidostilbene- 2,2-disulfonic acidsodium salt, and sodium -(a-phenylhydrazone).

In addition, photographic materials and elements utilizing the presentcyan dye-forming couplers can usefully contain brightners, such asstilbenes, triazines, etc., spectral sensitizing dyes, supersensitizingaddenda, and also absorbing and filter dyes as summarized, for instance,on page 109 in sections XIV, XV and XVI of Product Licensing IndexVolume 92 (Dec. 1971 Suitable light-sensitive emulsions for purposes ofthe present invention can also contain speed-increasing compounds of thequaternary ammonium and polyethylene gylcol type as found, for instance,in U.S. Pat. Nos. 2,271,623, 2,288,226, 2,334,864 and 2,708,162.

This invention is further described, although not limited, by thefollowing examples:

EXAMPLE I (COMPOUND NO. 1)

grams (.5 mole) of 1,7-dihydroxynaphthylene is refluxed for 48 hours ina-xylene with 126 grams of noctadecyl mercaptan in the presence of acatalytic amount of p-toluenesulfonic acid. The water byproduct is thenremoved from a Dean-Stark tube and the naphtholic product removed andidentified as 1 hydroxy-7-octadecylthio-naphthylene. m.p. 7072C..

EXAMPLE ll (COMPOUND NO. 8)

A. 140 ml of acetic anhydride is slowly added to 70 grams of 1hydroxy-7-octadecylthio naphthylene (Example I) with stirring at 120Cfor 4 hours. After cooling, the 1-acetoxy-7-octadecylthio naphthyleneproduct is separated out (ref. reaction 2 supra).

B. To .2 mole of the 1-acetoxy-7-octadecylthio intermediate product of(A) dissolved in acetic acid is added .4 mole of H 0 and the reactionmixture agitated at -100C. for about 1 hour to obtain the corresponding7-alkylsulfonyl derivative (m.p. 92-93.5C); this compound is thenhydrolyzed with 10 percent KOl-I-ethyl alcohol solution at 45C. toobtain the 7-octadecylsulfonyl-l-naphthol product; m.p. 90.5C.-9l .5C.

EXAMPLE lll (COMPOUND NO. 7)

To .2 mole of the 1-acetoxy-7-octadecylthio naphthol of Example II (A)dissolved in acetic acid is added .2 mole of H 0, and the mixtureagitated at 50-55C. for 1 hour to obtain the corresponding7-alkylsulfinyl derivative (m.p. 81C82C); the derivative is thenhydrolyzed with 10 percent KOH-ethyl alcohol solution at 45C as inExample 11 to obtain the corresponding 7- octadecylsulfinyl- 1 -naphtholproduct; mp. 94-95.5C.

EXAMPLE IV (COMPOUNDS NO. 25-27) Starting with .5 mole of 1,6dihydroxynaphthylene and reacting with n-octadecyl mercaptan in thepresence of p-toluenesulfonic acid as in Example I, a compoundidentified as compound 25 (i.e. l-hydroxy-6- octadecylthio naphthylene;m.p. 7078C) is obtained. 70 Grams of this compound is converted into thecorresponding l-acetoxy-6-octadecylthio naphthylene derivative byreacting with acetic anhydride, and .4 mole of this product is dissolvedin acetic acid and reacted with .4 mole H 0 as in Example-11(8) toobtain a compound identified as compound 27. By reacting .2 mole ofacetic acid solution of 1-acetoxy-6-octadecylthio naphthylene with .2mole of H 0 and then hydrolyzing in the manner of Example 111, there isobtained the corresponding 1-hydroxy-6-octadecyl sulfinyl naphthylenederivative identified as compound 26.

EXAMPLE v (COMPOUND N0.

.1 Mole of compound No. l of Example I in a basic solution oftetrahydrofuran and methanol (m.p. 70-72C.) is slowly added to with anequimolar amount of p-methoxy benzenediazonium chloride obtained fromp-methoxyaniline diazotized in acidic solution with sodium nitrite toobtain a product identified as compound No. 5 (m.p. l1l114C.).

EXAMPLE VI (COMPOUND NO. 22)

.1 Mole of compound No. 2 of Example 11 is reacted with .1 mole ofdiazotized p-methoxyaniline as in Example V to obtain a productidentified as Compound 22 (m.p. 118-l20C.).

EXAMPLE VII (COMPOUND NO. 23)

.1 Mole of compound No. 7 of Example III is reacted with .1 mole ofdiazotized p-methoxyaniline as in Example V to obtain a productidentified as Compoun No. 23 (m.p. 9699C.).

EXAMPLE VIII (COMPOUND NO. 24)

.l Mole of 1-hydroxy-2-acetyl-7- octadecylthionaphthylene is reactedwith .1 mole of diazotized p-methoxyaniline as in Example V to obtain aproduct identified as Compound 24 (m.p. 12l-l23C.).

EXAMPLE IX (COMPOUND NO. 28)

By utilizing .1 mole of the corresponding l-hydroxy- 6-octadecylthionaphthylene of Example IV and reacting this compound with an equimolaramount of diazotized p-methoxy-aniline as in Example V, there isobtainable a compound identified as Compound No. 28.

EXAMPLE X Eight test film strips are prepared, comprising a supportlayer having a single gelatino-silver bromoiodide emulsion layer coatedthereon which contains 75 mg/ft of one of the following couplers:2-(2,5-di-tamylphenoxy)-butyl 1 carbamyl-I-naphthol (control: U.S. Pat.No. 2,474,293), compound 1, compound 7, or compound 8 (ref. Table Isupra). The emulsion is prepared by dissolving one of these couplersinto di-nbutylphthalate (39 mg/ft), the solution then being einulsifiedwith a percent aqueous gelatin solution in the presence of anemulsifying agent and the emulsion dispersed into a light-sensitivegelatino-silver bromoiodide emulsion containing 450 mg/ft gelatin and136 mg/ft silver. The emulsion coated test strips are sensitometricallyexposed and processed by using either developing solution A or B(described below), stop fixed, washed, silver bleached, washed, fixed,washed, and dried in the conventional manner. The test 14 strips aresubjected to the usual light fading and heat fading tests to determinethe stability characteristics of unreacted coupler and of thecorresponding image dyes. The results obtained are recorded in Table Ibe- Light Fading Tests a. The extent to which the image dyes faded underthe influence of light was determined by subjecting several processedcoatings to a simulated 21-day North skylight exposure (SANS) andrecording the resulting decrease in dye density in an area of thecoating having had an initial dye density of approximately 1.2. Thisdecrease in dye density is termed Light Fade and is recorded in terms ofdensity units in Table I below.

b. The extent to which unreacted coupler caused unwanted stain under theinfluence of light was determined by exposing several processed coatingsby the procedure described under (a) above and recording the resultingincrease in density to blue light (420 mp.) of a Dmin area of thecoating. This increase is termed Printout and is recorded in terms ofpercent density increase in Table I below.

Heat Fading Tests a. The extent to which the image dyes faded under theinfluence of heat and humidity was determined by subjecting severalprocessed coatings for 1 week to a temperature of 140F at a relativehumidity of percent. The decrease in image dye density, termed HeatFade, was measured by the method described in section (a) under LightFading Tests. It is recorded in terms of density units in Table I below.

b. The effect of heat on unreacted coupler was determined by subjectingseveral coatings to the heat and humidity conditions cited above anddetermining the increase in density, termed Yellowing, by the methoddescribed in section (b) under Light Fading Tests. The obtained valuesare recorded in terms of percent density increase in Table I below.

TABLE I Light Heat Fade Fade Print YELL Compound Developer (LF (HF 2 OutDens. No. Solution Dmax max 21 days) weeks) (PO) Increase) Control A 3.00 699 .05 l 2 16% 8 a 2.78 688 .05 +93 15% 10 1 A 1.78 650 .11 +.l0 B1.35 625 .08 +.09 7 A 1.81 648 .11 +.02 9% 9 B 1.85 638 .09 +.04 9% 9 8A 3.08 653 .09 01 8% 10 B 2.21 s10 .05 +16 8% 13 This invention has beendescribed in detail with particular reference to a preferred embodimentthereof, but it will be understood that variations and modifications canbe effected within the spirit and scope of the invention as describedhereinabove, and as defined in the appended claims.

We claim:

I. A photographic silver halide emulsion containing a non-diffusiblea-naphtholic cyan dye-forming coupler with an alkylthio, alkylsulfonyl,or alkylsulfinyl substituent having at least 12 carbon atoms substitutedin the B ring of the a-naphtholic coupler.

2. A photographic silver halide emulsion containing at least onea-naphtholic cyan dye-forming coupler of the formula R(L)(NAOL) wherein(NAOL) is an unballasted or lightly ballasted a-naphtholic cyandye-forming coupler moiety;

R is an alkyl group having 12-22 carbon atoms;

L represents S-,

the R'(L)- radical being attached to -(NAOL) at the B ring.

3. A photographic silver halide emulsion containing at least one cyandye-forming coupler of the formula wherein R' is an alkyl group of l2-22carbon atoms;

L represents -S,

R is a hydrogen atom; a halo group; an amino group; an alkyl carbonylgroup of two to 12 carbon atoms; an arylcarbonyl group in which ringsubstituent groups total zero-l 2 carbon atoms; or a carbamyl group ofthe formula in which R is defined as a hydrogen atom or an alkyl R isdefined as a hydrogen atom or as a coupling off group.

4. An emulsion of claim 3 wherein R' is an alkyl group of 13-18 carbonatoms; and

R is a hydrogen atom or a carbamyl group defining R as hydrogen and R asan alkyl group of one to 18 carbon atoms. 5. An emulsion of claim 3wherein R is a hydrogen atom, a sulfonamido group or an arylazo group.

6. A photographic silver halide emulsion containing at least one cyandye-forming coupler of the formula H OH R S wherein R is defined as analkyl group having I2 22 carbon atoms;

R is a hydrogen atom, a halo group, or an alkyl carbonyl group havingtwo to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; athiocyano group; an alkoyloxy group of two to 10 carbon atoms; aphenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthiogroup; a heterocycloxy group or its thioanalog in which theheterocycloxy group or its thioanalog has a 5-6 membered heterocyclicring nucleus;

N=NR in which R is defined as a phenyl group, a naphthyl group, acarbon-containing heterocyclic group having 56 membered heterocyclicring nucleus; or NHSO R in which R is defined as an alkyl group, aphenyl group, or a naphthyl group.

7. A photographic silver halide emulsion containing at least one cyandye-forming coupler of the formula 0 at OH wherein R is defined as analkyl group having l2-22 carbon atoms;

R is a hydrogen atom, a halo group, or an alkyl carbonyl group havingtwo to l2 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; athiocyano group; an alkoyloxy group of two to 10 carbon atoms; aphenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthiogroup; a heterocycloxy group or its thioanalog in which theheterocycloxy group or its thioanalog has a 5-6 membered heterocyclicring nucleus;

N=NR in which R is defined as a phenyl group, a naphthyl group, acarbon-containing heterocyclic group having 5-6 membered heterocyclicring nu- 17 cleus; or -NHSO R" in which R is defined as an alkyl group,a phenyl group, or a naphthyl group. 8. A photographic silver halideemulsion containing at least one cyan dye-forming coupler of the formulawherein R is defined as an alkyl group having 12-22 carbon atoms; I

R is a hydrogen atom, a halo group, or an alkyl carbonyl group havingtwo to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; athiocyano group; an alkoyloxy group of two to 10 carbon atoms; aphenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthiogroup; a heterocycloxy group or its thioanalog in which theheterocycloxy group or its thioanalog has a 5-6 membered heterocyclicring nucleus; N=N-R in which R is defined as a phenyl group, a naphthylgroup, a carboncontaining heterocyclic group having 5-6 memberedheterocyclic ring nucleus; or NHSO -R in which R" is defined as an alkylgroup, a phenyl group, or a naphthyl group.

9. A color photographic silver halide emulsion of claim 3 wherein R isdefined as a p-alkoxy phenyl azo group in which the alkoxy moietycontains one to 10 carbon atoms.

10. A color photographic silver halide emulsion containing7-octadecylthio-l-naphthol as a coupler.

l l. A color photographic silver halide emulsion containing7-octadecylsulfinyl-l-naphthol as a coupler.

12. A color photographic silver halide emulsion containing7-octadecylsulfonyl-l-naphthol as a coupler.

13. A color photographic silver halide emulsion containing2-acetyl-7-octadecylsulfony1-l-naphthol as a 4 coupler.

14. A color photographic silver halide emulsion containing2-(Abutylcarbamyl 7-hexadecylthio-l-naphthol as a coupler.

15. A color photographic element comprising a support layer havingcoated thereon at least one gelatino- 5 wherein -(NAOL) is anunballasted or lightly ballasted a-naphtholic cyan dye-forming couplermoiety; R is an alkyl group having 12-22 carbon atoms; L represents :S-,

wherein R is an alkyl group of 12-22 carbon atoms; L represents -S-,

O 0 II 11 SO or S-;

R is a hydrogen atom; a halo group; an amino group; an alkyl group; analkyl carbonyl group of two to 12 carbon atoms; an arylcarbonyl group inwhich ring substituent groups total zero-12 carbon atoms; or a carbamylgroup of the formula in which R is defined as a hydrogen atom or analkyl group not exceeding three carbon atoms; and

R is defined as a hydrogen atom; an alkyl group not exceeding 18 carbonatoms; an aryloxy alkyl group or an arylalkyl group in which the alkylmoieties contain one to four carbon atoms; an aryl group having assubstituents a member of not more than 16 carbon atoms selected from thegroup consisting of a carboxy, an alkoxy and an alkyl sulfonyl group; or

a carbon-containing heterocyclic group having a 5-6 memberedheterocyclic ring nucleus with at least one heteronitrogen, oxygen orsulfur atom in the nucleus; and

R is defined as a hydrogen atom or as a coupling off group.

18. A color photographic element of claim 17 in which the cyandye-forming coupler is characterized by defining R as an alkyl group of13-18 carbon atoms; and R as a hydrogen atom or a carbamyl groupdefining R as hydrogen and R as an alkyl group of one to 18 carbonatoms.

19. A color photographic element of claim 17 in which the cyandye-forming coupler is characterized by defining R as a hydrogen atom ora sulfonamido group.

20. A color photographic element comprising a support layer,-at leastone gelatino-silver halide emulsion and at least one cyan dye-formingcoupler of the formula I V RLS OH wherein R is defined as an alkyl grouphaving 12-22 carbon atoms;

R is a hydrogen atoms, a halo group, or an alkyl carbonyl group havingtwo to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; athiocyano group; an alkoyloxy group of two to l carbon atoms; aphenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthiogroup; a heterocycloxy group or its thioanalog in which theheterocycloxy group or its thioanalog has a 5-6 membered heterocyclicring nucleus;

N=NR in which R is defined as a phenyl group,

a naphthyl group, a carbon-containing heterocyclic group having 5-6membered heterocyclic ring nucleus; or ---Nl-lSO R in which R is definedas an alkyl group, a phenyl group, or a naphthyl group.

21. A color photographic element comprising a support layer, at leastone gelatino-silver halide emulsion and at least one cyan dye-formingcoupler of the formula 0H R S RI I Hi wherein R is defined as an alkylgroup having 12-22 carbon atoms;

R is a hydrogen atom, a halo group, or an alkyl carbonyl group havingtwo to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; athiocyano group; an alkoyloxy group of two to carbon atoms; a phenyloxygroup; a naphthoxy group; a phenylthio group; a naphthylthio group; aheterocycloxy group or its thioanalog in which the heterocycloxy groupor its thioanalog has a 5-6 membered heterocyclic ring nucleus;

---N=N-R in which R is defined as a phenyl group, a naphthyl group, acarbon-containing heterocyclic group having 5-6 membered heterocyclicring nucleus; or -NH--SO R in which R is defined as an alkyl group, aphenyl group, or a naphthyl group.

22. A color photographic element comprising a support layer, at leastone gelatino-silver halide emulsion and at least one cyan dye-formingcoupler of the formula II 0H R1S wherein R is defined as an alkyl grouphaving 12-22 carbon atoms;

R is a hydrogen atom, a halo group, or an alkyl carbonyl group havingtwo to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; athiocyano group; an alkoyloxy group of two to 10 carbon atoms; aphenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthiogroup; a heterocycloxy group or its thioanalog in which theheterocycloxy group or its thioanalog has a 5-6 membered heterocyclicring nucleus;

N=NR in which R is defined as a phenyl group,

a naphthyl group, a carbon-containing heterocyclic group having 5-6membered heterocyclic ring nucleus; or --Nl-lSO R in which R is definedas an alkyl group, a phenyl group, or a naphthyl group.

23. A color photographic element of claim 17 wherein R is defined as ap-alkoxy phenyl azo group in which the alkoxy moiety contains one to 10carbon atoms.

24. A color photographic element comprising a support layer, at leastone gelatino-silver halide emulsion and 7-octadecylthio-l-naphthol as acoupler.

25. A color photographic element comprising a support layer, at leastone gelatino-silver halide emulsion and 7-octadecylthio-l-naphthol as acoupler.

26. A color photographic element comprising a sup port layer, at leastone gelatino-silver halide emulsion and 7-octadecylsulfonyl-l-naphtholas a coupler.

27. A color photographic element comprising a support layer, at leastone gelatino-silver halide emulsion and2-acetyl-7-octadecylsulfonyl-l-naphthol as a coupler.

28. A color photographic element comprising a support layer, at leastone gelatino-silver halide emulsion and 2-(A butylcarbamyl7-hexadecyl-l-naphthol as a coupler.

2. A photographic silver halide emulsion containing at least one Alpha-naphtholic cyan dye-forming coupler of the formula R1-(L)-(NAOL)wherein -(NAOL) is an unballasted or lightly ballasted Alpha -naphtholiccyan dye-forming coupler moiety; R1 is an alkyl group having 12-22carbon atoms; L represents -S-,
 3. A photographic silver halide emulsioncontaining at least one cyan dye-forming coupler of the formula
 4. Anemulsion of claim 3 wherein R1 is an alkyl group of 13-18 carbon atoms;and R2 is a hydrogen atom or a carbamyl group defining R4 as hydrogenand R5 as an alkyl group of one to 18 carbon atoms.
 5. An emulsion ofclaim 3 wherein R3 is a hydrogen atom, a sulfonamido group or an arylazogroup.
 6. A photographic silver halide emulsion containing at least onecyan dye-forming coupler of the formula
 7. A photographic silver halideemulsion containing at least one cyan dye-forming coupler of the formula8. A photographic silver halide emulsion containing at least one cyandye-forming coupler of the formula
 9. A color photographic silver halideemulsion of claim 3 wherein R3 is defined as a p-alkoxy phenyl azo groupin which the alkoxy moiety contains one to 10 carbon atoms.
 10. A colorphotographic silver halide emulsion containing7-octadecylthio-1-naphthol as a coupler.
 11. A color photographic silverhalide emulsion containing 7-octadecylsulfinyl-1-naphthol as a coupler.12. A color photographic silver halide emulsion containing7-octadecylsulfonyl-1-naphthol as a coupler.
 13. A color photographicsilver halide emulsion containing2-acetyl-7-octadecylsulfonyl-1-naphthol as a coupler.
 14. A colorphotographic silver halide emulsion containing 2-( Delta butylcarbamyl7-hexadecylthio-1-naphthol as a coupler.
 15. A color photographicelement comprising a support layer having coated thereon at least onegelatino-silver halide emulsion layer containing a non-diffusible Alpha-naphtholic cyan dye-forming coupler with an alkylthio, alkylsulfonyl,or alkylsulfinyl substituent having at least 12 carbon atoms substitutedin the Beta ring of the Alpha naphtholic coupler.
 16. A colorphotographic element comprising a support layer having coated thereon atleast one gelatino-silver halide emulsion layer containing at least oneAlpha -naphtholic cyan dye-forming coupler of the formula R1-(L)-(NAOL)wherein -(NAOL) is an unballasted or lightly ballasted Alpha -naphtholiccyan dye-forming coupler moiety; R1 is an alkyl group having 12-22carbon atoms; L represents -S-,
 17. A color photographic elementcomprising a support layer, at least one gelatino-silver halide emulsionlayer applied thereto, and at least one cyan dye-forming coupler of theformula
 18. A color photographic element of claim 17 in which the cyandye-forming coupler is characterized by defining R1 as an alkyl group of13-18 carbon atoms; and R2 as a hydrogen atom or a carbamyl groupdefining R4 as hydrogen and R5 as an alkyl group of one to 18 carbonatoms.
 19. A color photographic element of claim 17 in which the cyandye-forming coupler is characterized by defining R3 as a hydrogen atomor a sulfonamido group.
 20. A color photographic element comprising asupport layer, at least one gelatino-silver halide emulsion and at leastone cyan dye-forming coupler of the formula
 21. A color photographicelement comprising a support layer, at least one gelatino-silver halideemulsion and at least one cyan dye-forming coupler of the formula
 22. Acolor photographic element comprising a support layer, at least onegelatino-silver halide emulsion and at least one cyan dye-formingcoupler of the formula
 23. A color photographic element of claim 17wherein R3 is defined as a p-alkoxy phenyl azo group in which the alkoxymoiety contains one to 10 carbon atoms.
 24. A color photographic elementcomprising a support layer, at least one gelatino-silver halide emulsionand 7-octadecylthio-1-naphthol as a coupler.
 25. A color photographicelement comprising a support layer, at least one gelatino-silver halideemulsion and 7-octadecylthio-1-naphthol as a coupler.
 26. A colorphotographic element comprising a support layer, at least onegelatino-silver halide emulsion and 7-octadecylsulfonyl-1-naphthol as acoupler.
 27. A color photographic element comprising a support layer, atleast one gelatino-silver halide emulsion and2-acetyl-7-octadecylsulfonyl-1-naphthol as a coupler.
 28. A colorphotographic element comprising a support layer, at least onegelatino-silver halide emulsion and 2-( Delta butylcarbamyl7-hexadecyl-1-naphthol as a coupler.